Polyolefin catalyst component using non-covalent interactions

ABSTRACT

A compound of formula I:  
                 
 
     (wherein R 1 -R 7 , M, T, X, Y, m and n are defined herein). The compound, when combined with a suitable activator, is active for the polymerization of olefins. For specific combinations of the R 1 -R 7  and T groups, these catalysts can engage in weak attractive non-covalent interactions with the polymer chain.

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/404,452, filed Aug. 19, 2002, the entire disclosurebeing incorporated herein by reference.

FIELD OF THE INVENTION

[0002] This invention relates to a non-metallocene catalyst systemcomprising a metal complex and a suitable activator, which is highlyactive in the olefin polymerization process.

BACKGROUND OF THE INVENTION

[0003] Polyolefins have been made chiefly using conventional Zieglercatalyst systems, but in recent years, the replacement of Zieglercatalysts by metallocene-based systems has begun. Metallocene catalysts,which are transition metal compounds bearing one or morecyclopentadienyl (“Cp”) ring ligand(s), are typically used withaluminoxanes as activators to give very high activities. In many cases,the transition metal is titanium or zirconium. Metallocene polyolefincatalysts provide solutions to many of the problems encountered forZiegler catalysts (such as low activity, staining and instability fromresidual catalysts, broad molecular distribution, and ineffectiveco-monomer incorporation) and are well known in the art.

[0004] The commercialization of metallocene catalysts for olefinpolymerization has resulted in great interest in the design ofnon-metallocene homogeneous catalysts. A new generation of catalysts maydisplay improved activity and offer a superior route to knownpolyolefins and mray also lead to processes and products that areoutside the capability of metallocene catalysts. In addition,substituted analogues of non-cyclopentadienyl ligands and compounds maybe easier to synthesize and hence non-metallocene catalysts may be morecost-effective.

[0005] Non-metallocene polyolefin catalysts with at least one phenolategroup are well known in the art (see U.S. Pat. Nos. 4,452,914 toColeman, III, et al. and 5,079,205 to Canich). U.S. Pat. No. 5,840,646to Katayama et al. and EP 0 606 125 B1 assigned to Shell InternationalResearch disclose bidentate bis(phenolate) titanium and zirconiumcatalysts for olefin polymerization.

[0006] Multidentate anionic oxygen- and nitrogen-based groups haveattracted attention as ligands for non-metallocene polyolefin catalysts.In termns of bidentate ligands, pyridinoxy and quinolinoxy ligands havebeen reported (see, e.g., U.S. Pat. No. 5,637,660 to Nagy et al.; U.S.Pat. No. 5,852,146 to Reichle et al.; U.S. Pat. No. 6,020,493 to Liu;Bei et al., Organometallics 17:3282 (1997); and Tsukahara et al.,Organometallics 16:3303 (1997).)

[0007] Tetradentate anionic ligands containing amine-bis(phenolate)groups (phenolate being an aromatic hydroxyl group) have recently beenapplied in polyolefin catalysts by Kol, Goldschmidt and coworkers (seeU.S. Pat. No. 6,333,423 to Kol et al.; Tshuva et al., Chem. Commun. 379(2000) and Chem. Commun. 2120 (2001)). Shao et al., Organometallics19:509 (2000) describe zirconium complexes of tridentate chelatingamine-bis(alkoxide) (alkoxide being an aliphatic hydroxyl group) ligandsas polyolefin catalysts, but the observed activity is very low. Bouwkampet al., Organometallics 17:3645 (1998) described zirconium complexeswith symmetric tridentate amine-bis(σ-aryl) dianionic ligands aspolyolefin catalysts, but the observed activities are only moderate.

[0008] Hence there is a need in the art for new olefin polymerizationcatalysts, particularly catalysts containing multidentate ligands of thepyridine-phenolate type. There is also a need in the art for thediscovery and optimization of non-metallocene polyolefin catalystscontaining unsymmetric or chiral ligands, because this may result in thestereoselective polymerization of 1-olefins (alpha-olefins) and lead topolyolefins with distinctive morphology and properties.

[0009] Metallocene catalysts, especially those that are chiral and/or oflow symmetry, are used to produce stereoregular polyolefins (see, e.g.,G. W. Coates, Chem. Rev. 100:1223 (2000), and references cited therein).These catalysts depend on simple steric effects to controlstereoselectivity.

[0010] Use of weak non-covalent attractive interactions to achievestereoselectivity has not been established in the art. Use of weaknon-covalent attractive interactions to stabilize reactive intermediatesin olefin polymerization has not been established in the art.

SUMMARY OF THE INVENTION

[0011] This invention relates to a polyolefin catalyst system, whichcomprises a cyclometallated catalyst containing a Group 3 to 10 metalatom or lanthanide metal and a suitable activator.

[0012] This invention also relates to cyclometallated catalysts offormula I shown below:

[0013] wherein:

[0014] R¹-R⁷ are each independently —H, -halo, —NO₂, —CN,-(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl, or-heteroaryl, each of which may be unsubstituted or substituted with oneor more -R⁸ groups; or two R¹-R⁷ may be joined to form cyclic group;

[0015] R⁸ is -halo, -(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —NO₂,—CN, —Si((C₁-C₃₀)hydrocarbyl)₃, —N((C₁-C₃₀)hydrocarbyl)₂,-(C₁₋₃₀)heterohydrocarbyl, -aryl, or -heteroaryl;

[0016] T is —CR⁹R¹⁰— wherein R⁹and R¹⁰ are defined as for R¹ above;

[0017] E is a Group 16 element;

[0018] M is a metal selected from the group consisting of metallic Group3 to Group 10 elements and the Lanthanide series elements;

[0019] m is the oxidation state of the M;

[0020] X is defined as R¹ above excluding —H, wherein X is bonded to M;

[0021] Y is neutral ligand datively bound to M; and

[0022] n is an integer ranging from 0 to 5.

[0023] This invention further relates to cyclometallated catalysts offormula II shown below:

[0024] wherein:

[0025] R¹-R¹¹ each independently —H, -halo, —NO₂, —CN,-(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl,-heteroaryl, each of which may be unsubstituted or substituted with oneor more -R¹² groups; or two R¹-R⁷ may be joined to form a cyclic group;

[0026] each R¹² is independently -halo, —NO₂, —CN, -(C₁-C₃₀)hydrocarbyl,—O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl, or-heteroaryl;

[0027] E is a Group 16 element;

[0028] M is a metal selected from the group consisting of metallic Group3 to Group 10 elements and the Lanthanide series elements;

[0029] m is the oxidation state of the M;

[0030] X is R¹ excluding —H, wherein X is bonded to M;

[0031] Y is neutral ligand datively bound to M; and

[0032] n is an integer ranging from 0 to 5.

[0033] In one embodiment, the cyclometallated catalysts of formula (I)and/or formula (II) are combined with a suitable activator to form anolefin polymerization catalyst.

[0034] In one embodiment, the cyclometallated catalysts of formula (I)and/or formula (II) are combined with a suitable activator to form acatalyst useful for the stereoselective polymerization of 1-olefins.

[0035] In one embodiment, the R¹-R⁷ and T groups in formula I, and theR¹-R¹¹ groups in formula II exhibit weak attractive non-covalentinteractions with the polymer chain.

[0036] The invention further relates to methods of olefin polymerizationcomprising cyclometallated catalysts of formula I and/or II. Suchpolymerization processes include but are not limited to gas,high-pressure liquid, slurry, bulk, solution, or suspension-phasetechniques, and combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[0037]FIG. 1 shows the ¹H NMR spectrum of Catalyst 3 in C₆D₆, (400 MHz,300 K) (*=C₆D₆, +=residual toluene). FIG. 1 also shows the ¹NMR spectrafor the diastereotopic methylene hydrogens of the benzyl group ofCatalyst 3 in C6D₆, CD₂Cl₂ and d₈-THF, demonstrating the effect ofsolvent polarity on the chemical shift and splitting pattern, where thedesignation “{¹⁹F }” means the NMR spectrum was run in ¹⁹F decoupledmode.

[0038]FIG. 2 shows the ¹⁹F[¹H] (front) and ¹⁹F{¹H} (back; horizontalscale displaced for clarity) NMR spectra (376 MHz, C₆D₆, 300 K) ofCatalyst 3. The designation “[ ]” means that the NMR spectrum was run incoupled mode (i.e., ¹⁹F and ¹H coupled NMR).

[0039]FIG. 3 shows the ¹H NMR spectra (400 MHz, 300 K) of Catalyst 4,illustrating the effects of ¹⁹F-decoupling and solvent polarity upon thediastereotopic methylene hydrogens (*=deuterated solvent, +=residualtoluene) for C₆D₆, CD₂Cl₂ and d₈-THF.

[0040]FIG. 4 shows the X-ray crystal structure of Catalyst 1.

[0041]FIG. 5 shows the X-ray crystal structure of Catalyst 2.

[0042]FIG. 6 shows the X-ray crystal structure of Catalyst 3.

[0043]FIG. 7 shows the X-ray crystal structure of Catalyst 5.

[0044]FIG. 8 shows the ¹H (400 MHz) and ¹⁹F (376 MHz, CF₃ region, ppmaxis displaced for clarity) NMR spectra (CD₂Cl₂+d₈-THF, 300 K) forη²-CH₂Ph cation derived from reaction of Catalyst 3 with B(C₆F₅)₃,demonstrating effects of ¹⁹F- and ¹H-decoupling respectively(*=deuterated solvents).

DETAILED DESCRIPTION OF THE INVENTION

[0045] As used herein, the term “-(C₁-C₃₀)hydrocarbyl” refers to ahydrocarbon group containing from 1-30 carbon atoms. Non-limitingexamples of -(C₁-C₃₀)hydrocarbyl groups include -(C₁-C₃₀)alkanes;-(C₁-C₃₀)alkenes; -(C₁-C₃₀)alkynes.

[0046] As used herein, the term “-(C₁-C₃₀)heterohydrocarbyl” refers to a-(C₁-C₃₀)hydrocarbyl in which one or more of the carbon atoms have beenreplaced with an atom other than carbon or hydrogen, i.e., a heteroatom,e.g., N, P, Si, Ge, O and S.

[0047] As used herein the term “heteroaryl” refers to an aryl groupcontaining an atom other than carbon in the aryl ring. Non-limitingexamples of heteroaryls include pyrrole, pyridine, and the like

[0048] As used herein, the phrase “alkylaluminum compound” refers to acompound containing a bond between an organic radical and an aluminummetal.

[0049] As used herein, the phrase “homopolymerization process” means aprocess for forming a polyolefin using only one type of monomer. Theresultant polymer is referred to as a “homopolymer.”

[0050] As used herein, the phrase “copolymerization process” means apolymerization process in which two or more different olefin monomersare incorporated into the same polymer to form a “copolymer.”

[0051] As used herein, the phrase “cyclometallated catalyst” means acompound in which the metallic Group 3 to Group 10 or Lanthanideelements is part of a ligand-metal ring system containing from 4 to 8atoms, wherein the ligand-metal ring system contains a metal-carbon[M-C] bond. The ring system is stabilized due to the chelate effect,i.e., the ligand is coordinated to the metal by at least two bonds.

[0052] As used herein, the phrase “neutral ligand” refers to anuncharged molecule, which may be either a mono- or bidentate molecule,that forms a dative bond between a ligand atom and the metal atom.Non-limiting examples of neutral ligands include N-donor ligands, e.g.,amines, tetrahydropyrrole, pyrrole, piperazine and pyridine; P-donorgroups, e.g., phosphine, tetrahydrophosphole, and phospole; O-donorgroups include, e.g., ethers including dimethyl ether, diethyl ether,di-propyl ether, di-butyl ether, di-pentyl ether, tetrahydrofuran anddioxane; and glymes, e.g., dimethoxyethane

[0053] As used herein, the phrase “non-nucleophilic anions” refers tothe anion portion of an activator salt, which anion is a weak or poorLewis base.

[0054] As used herein, the term “olefin” refers to a hydrocarbonmolecule containing at least one carbon-carbon double bond such as,e.g., ethylene. The olefin may be unsubstituted or substituted, providedthe substituents do not prevent the polymerization of the olefin.

[0055] As used herein, the phrase “Group 16 element” refers to oxygen,sulfur, selenium and tellurium.

[0056] As used herein, the term “halide” refers to fluoride, chloride,bromide and iodide.

[0057] This invention relates to a polyolefin catalyst system comprisinga cyclometallated catalyst and a suitable activator, wherein the metalis a Group 3 to 10 transition metal or lanthanide metal. [Acyclometallated catalyst contains a metal-carbon [M-C] bond as part of a[X-M-C] ring system which is stabilized due to the chelate effect, whereX can be any element or group that is capable of bonding to the metal.]Preferably the metal is Ti, Zr or Hf. Preferably the metal is Ti, Zr orHf.

[0058] This invention also relates to cyclometallated catalysts offormula I:

[0059] wherein:

[0060] R¹-R⁷ are each independently —H, -halo, —NO₂, —CN,-(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl, or-heteroaryl, each of which may be unsubstituted or substituted with oneor more -R⁸ groups; or two R¹-R⁷ may be joined to form a cyclic group;

[0061] R⁸ is -halo, -(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —NO₂,—CN, —Si((C₁-C₃₀)hydrocarbyl)₃, —N((C₁-C₃₀)hydrocarbyl)₂,-(C₁-C₃₀)heterohydrocarbyl, -aryl, or -heteroaryl;

[0062] T is —CR⁹R¹⁰— wherein R⁹and R¹⁰ are defined as for R¹ above;

[0063] E is a Group 16 element;

[0064] M is a metal selected from the group consisting of metallic Group3 to Group 10 elements and the Lanthanide series elements;

[0065] m is the oxidation state of the M;

[0066] X is R¹ excluding —H, wherein X is bonded to M;

[0067] Y is neutral ligand datively bound to M; and

[0068] n is an integer ranging from 0 to 5.

[0069] In one embodiment, the invention relates to catalysts of formulaI wherein M is titanium, zirconium or haffiium.

[0070] In one embodiment, the invention relates to catalysts of formulaI wherein E is —O— such that a tridentate phenolate-pyridine-carbanionligand is coordinated to M.

[0071] In one embodiment, the invention relates to catalysts of formulaI wherein X is —CH₃, —CH₂CH₃, -benzyl, -halo. Preferably, X is -benzyl,or -chloride.

[0072] In one embodiment, the invention relates to catalysts of formulaI wherein Y is absent.

[0073] In one embodiment, the invention relates to catalysts of formulaI wherein Y is an N-donor ligand, P-donor ligand, As-donor ligand,O-donor ligand or S-donor ligand. Non-limiting examples of neutralligands include N-donor ligands, e.g., amines, tetrahydropyrrole,pyrrole, piperazine and pyridine; P-donor groups, e.g.,trialkyphosphine, dialklylarylphosopine, alklydiarylphosphine, andtriarylphosphine, in which one or more of the alkyl or aryl groups maybe replaced by an alkoxy or aryloxy group to form a phosphite; As-donorgroup include, e.g., trialkylarsine, dialklylarylarsine,alklydiarylarsine, and triarylarsine, in which one or more of the alkylor aryl groups may be replaced by an alkoxy or aryloxy group to form anarsite; O-donor groups, e.g., ethers including dimethyl ether, diethylether, di-propyl ether, di-butyl ether, di-pentyl ether,tetrahydrofuran, dioxane; and glymes , e.g., dimethoxyethane. In apreferred embodiment, Y is tetrahydrofiran or diethyl ether. Morepreferably, Y is tetrahydrofuran.

[0074] In one embodiment, the invention relates to catalysts of formulaI, wherein the R¹-R⁷ and T groups exhibit weak attractive non-covalentinteractions with the polymer chain. Without being bound by theory, itis believed that weak non-covalent attractive interactions must avoidinteractions that might otherwise disrupt the polymerization processand/or the turnover rate. Evidence for intramolecular weak non-covalentattractive interactions have been obtained for the non-metallocenepolyolefin catalysts described herein.

[0075] This invention also relates to non-metallocene catalysts offormula (II):

[0076] wherein:

[0077] R¹-R¹¹ each independently —H, -halo, —NO₂, —CN,-(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl,-heteroaryl, each of which may be unsubstituted or substituted with oneor more -R¹² groups; or two R¹-R⁷ may be joined to form a cyclic group;

[0078] each R¹² is independently -halo, —NO₂, —CN, -(C₁-C₃₀)hydrocarbyl,—O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl, or-heteroaryl;

[0079] E is a Group 16 element;

[0080] M is a metal selected from the group consisting of metallic Group3 to Group 10 elements and the Lanthanide series elements;

[0081] m is the oxidation state of the M;

[0082] X is R¹ excluding —H, wherein X is bonded to M;

[0083] Y is neutral ligand datively bound to M; and

[0084] n is an integer ranging from 0 to 5.

[0085] In one embodiment, the invention relates to catalysts of formulaII wherein M is titanium, zirconium or hafnijum.

[0086] In one embodiment, the invention relates to catalysts of formulaII wherein E is —O— such that a tridentate phenolate-pyridine-carbanionligand is coordinated to M.

[0087] In one embodiment, the invention relates to catalysts of formulaII wherein X is —CH₃, —CH₂CH₃, -benzyl or -halo. Preferably, X is-benzyl or -chloride.

[0088] In one embodiment, the invention relates to catalysts of formulaII wherein Y is absent.

[0089] In one embodiment, the invention relates to catalysts of formulaII wherein Y is as defined above for the catalysts of formula I. In apreferred embodiment, Y is tetrahydrofuran.

[0090] In one embodiment, the invention relates to catalysts of formulaII wherein M is Zr; R¹ and R³ are —C(CH₃)₃; R² and R⁴-R¹¹ are -H; E is—O—; m is 4; X is —CH₂(C₆H₅); and n is 0.

[0091] In one embodiment, the invention relates to catalysts of formulaII wherein M is Zr; R¹ and R³ are —C(CH₃)₃; R² and R⁴-R¹¹ are —H; E is—O—; m is 4; X is —Cl; n is 1; and Y is -tetrahydrofuran.

[0092] In one embodiment, the invention relates to catalysts of formulaII wherein M is Zr; R¹ and R³ are —C(CH₃)₃; R⁹ and R¹¹ are —CF₃; R²,R⁴-R⁸ and R¹⁰ are —H; E is —O—; m is 4; X is —CH₂(C₆H₅); and n is 0.

[0093] In one embodiment, the invention relates to catalysts of formulaII wherein M is Ti; R¹ and R³ are —C(CH₃)₃; R⁹ and R¹¹ are —CF₃; R²,R⁴-R⁸ and R¹⁰ are —H; E is —O—; m is 4; X is —CH₂(C₆H₅); and n is 0.

[0094] In one embodiment, the invention relates to catalysts of formulaII wherein M is Zr; R¹ and R³ are —C(CH₃)₃; R⁹ is —CF₃; R², R⁴-R⁸ andR¹⁰-R¹¹ are —H; E is —O—; m is 4; X is —CH₂(C₆H₅); and n is 0.

[0095] In one embodiment, the invention relates to catalysts of formulaII wherein M is Zr; R¹ and R³ are —C(CH₃)₃; R⁹ is —CF₃; R¹¹ is —F; R²,R⁴-R⁸ and R¹⁰ are —H; E is —O—; m is 4; X is —Cl; n is 1; and Y istetrahydrofuran.

[0096] In one embodiment, the invention relates to catalysts of formulaII wherein the R¹-R¹¹ groups in formula II exhibit weak attractivenon-covalent interactions with the polymer chain. Without being bound bytheory, it is believed that weak non-covalent attractive interactionsmust avoid interactions that might otherwise disrupt the polymerizationprocess and/or the turnover rate. Evidence for intramolecular weaknon-covalent attractive interactions have been obtained for thenon-metallocene polyolefin catalysts described herein.

[0097] In one embodiment, the invention relates to a catalyst of formulaII (one non-limiting example being depicted as Catalyst 3 in Example 6)wherein M is Zr; E is —O—; X is -benzyl; R⁹ and R¹¹ are —CF₃; R¹ and R³are -tert-butyl; R^(2,4-8,10) are —H; and Y is absent. In thisembodiment, ¹H J(H . . . F) coupling of 3.3 Hz (¹H NMR, see FIG. 1) and²H J(C . . . F) coupling of 5.9 Hz (¹³C NMR) are observed between one ofthe benzyl —CH₂— protons and the —CF₃ group at R¹¹. Subsequent¹⁹F-decoupling of the ¹H NMR spectrum confirms this coupling. Similarly,while the coupling in the ¹⁹F[1H] NMR spectrum is not clearly resolved,the ¹⁹F{1H} spectrum undergoes significant narrowing for the downfieldresonance at −58.09 ppm for the —CF₃ group at R¹¹ only (FIG. 2). Theseobservations thus demonstrate the existence of intramolecular‘through-space’ coupling via weak non-covalent attractive [C—H . . .F—C] hydrogen bonding interactions. The effects of solvent polarity uponthis coupling have been probed, and ¹H J(H . . . F) values of 3.3 and3.1 Hz in C₆D₆ and CD₂Cl₂ respectively have been obtained, whereas ind8-THF the said coupling is unresolved yet still apparent (FIG. 1). Avirtually identical intramolecular [CH . . . FC] interaction is obtainedwhen a catalyst of formula II is used in which the Zr of Catalyst 3 isreplaced by Ti (one non-limiting example being depicted as Catalyst 4 inExample 7), as indicated by analogous NMR experiments (FIG. 3), althoughthe through-space coupling is slightly weaker (in C₆D₆: ^(1h)J_(HF) ca.2 Hz, ^(2h)J_(CF)=5.3 Hz).

[0098] This model can be applied to an active intermediate during olefinpolymerization, where intramolecular attractive weak interactions (e.g.C—H . . . F—C) can be envisaged between the functionalized ligand andpolymer chain. Use of said weak non-covalent interactions to modify ormanipulate catalytic reactivity and polymer properties has not beenestablished in the art. Use of said weak non-covalent interactions tostabilize reactive intermediates or to achieve stereoselectivity inolefin polymerization has not been established in the art. For example,these types of intramolecular weak non-covalent attractive interactionscan suppress H-transfer and chain termination processes duringpolymerization and may also afford highly stereoselective polymers.

[0099] The preparation of the desired ligands is versatile and can beachieved by modification of procedures described in the literature (see,e.g., Silva et al., Tetrahedron 53:11645 (1997); and Dietrich-Bucheckeret al., Tetrahedron 46: 503 (1990)).

[0100] Metallation of the substituted 2-(phenol)-6-arylpyridinesubstrates containing acidic protons can be accomplished by reactionwith basic metal reagents such as tetrabenzyltitanium(IV), Ti(CH₂Ph)₄,tetrabenzylzirconium(IV), Zr(CH₂Ph)₄, bisbenzylzirconium(IV) dichloride,Zr(CH₂Ph)₂Cl₂, and tetrabenzylhafnium(IV), Hf(CH₂Ph)₄, which isaccompanied by elimination of toluene and cyclometallation, i.e.,metal-carbon bond formation between metal and aryl group) readily occursat room temperature. The resultant metal complex contains aphenolate-pyridine-carbanion ligand which is chelated in a tridentatemeridional fashion. A neutral O-donor solvent, for exampletetrahydrofuran or diethyl ether, is added to the reaction mixture tofacilitate the isolation of the complex, in some instances in itssolvated form. As determined by ¹H NMR spectroscopy and in some case byX-ray crystallography, the two remaining halide or alkyl ligands are ina cis conformation, and this is important for the employment of thesecomplexes as polyolefin catalysts.

[0101] The present invention relates to a catalyst system comprising thecyclometallated catalysts of the invention and an activator. Generally,the activator converts the cyclometallated catalyst to a cationic activespecies. Suitable activators are well known in the art and include, butare not limited to, trimethylaluminum (TMA), triethylaluminum (TEA),tri-isobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminumdichloride, ethylaluminum dichloride, dimethylaluminum chloride,diethylaluminum chloride, aluminoxanes, and the like. Aluminoxanes areknown in the art as typically the oligomeric compounds that can beprepared by the controlled addition of water to an alkylaluminumcompound, for example trimethylaluminum. Examples of aluminoxanescompounds include methylaluminoxane (MAO), modified methylaluminoxane(MMAO), ethylaluminoxane, and diisobutylaluminoxane. In this invention,alkylaluminoxanes such as methylaluminoxane (MAO) are preferred. In thiscontext it should be noted that the term “alkylaluminoxane” as used inthis specification includes alkylaluminoxanes available commerciallywhich may contain a proportion, typically about 10 wt %, but optionallyup to 50 wt %, of the corresponding trialkylaluminum; for instance,commercial MAO usually contains approximately 10 wt % trimethylaluminum(TMA), whilst commercial MMAO contains both TMA and TIBA. Quantities ofalkylaluminoxane quoted herein include such trialkylaluminum impurities,and accordingly quantities of trialkylaluminum compounds quoted hereinare considered to comprise compounds of the formula AlR₃ additional toany AlR₃ compound incorporated within the alkylaluminoxane when present.

[0102] Suitable activators also include acid salts that containnon-nucleophilic anions. These compounds generally consist of bulkyligands attached to boron or aluminum. Non-limiting examples of suitableactivators include tetrakis(pentafluorophenyl)borate,dimethylphenylamrnonium tetra(pentafluorophenyl)borate, trityltetra(pentafluorophenyl)borate, and the like. Suitable activators alsoinclude trialkyl or triarylboron compounds such astris(pentafluorophenyl)boron, tris(pentabromophenyl)boron, and the like.Other suitable activators are described, for example, in U.S. Pat. Nos.5,064,802 and 5,599,761 to Turner.

[0103] In one embodiment, the activator is selected from the groupconsisting of trimethylaluminum, triethylaluminum, tri-isobutylaluminum,tri-n-octylaluminum, methylaluminum dichloride, ethylaluminumdichloride, dimethylaluminum chloride, diethylaluminum chloride,aluminoxanes, tetrakis(pentafluorophenyl)borate, dimethylphenylammoniumtetra(pentafluorophenyl)borate, trityl tetra(pentafluorophenyl)borate,tris(pentafluorophenyl)boron, tris(pentabromophenyl)boron, and mixturesthereof.

[0104] In the preparation of the catalysts of the present invention, thequantity of the activator to be employed is determined by routineexperimentation. It is found that the quantity employed is 0.1 to20,000, preferably 1 to 2000 of mole aluminum (or boron) per molecyclometallated compound.

[0105] In a preferred embodiment, the polyolefin catalyst of formula Iand/or formula II is combined with one of more of the above-namedactivators, or a mixture thereof, to form a cyclometallated catalystsystem that is active for olefin polymerization process.

[0106] The present invention further relates to methods for polymerizingan olefin using a cyclometallated catalyst system. Such polymerizationprocesses include, but are not limited to, gas-phase, high-pressureliquid, slurry, bulk, solution, or suspension-phase techniques, andcombinations thereof. Such processes can be used to performhomopolymerization and/or copolymerization of olefins.

[0107] Suitable olefins include one or more of ethylene, propylene,butenes, pentenes, hexenes, octenes, styrenes, 1,3-butadiene, norbomeneand the like, either substituted or unsubstituted, or combinationsthereof. Suitable substituents are those that will not preventpolymerization of the olefin. Non-limiting examples of suitable olefinsubstituents include -alkyl, -aryl and —Si(alkyl)₃.

[0108] In one embodiment, the olefin is selected from the groupconsisting of ethylene, propylene, 1-butene, 2-pentene, 1-hexene,1-octene, styrene, 1,3-butadiene, norbomene, and mixtures thereof.

[0109] In one embodiment, an olefin selected from the group consistingof ethylene, propylene, or a mixture thereof is copolymerized with anolefin selected from the group consisting of 1-butene, 1-hexene, and1-octene.

[0110] Preferably, the olefin is ethylene or 1-hexene.

[0111] In one embodiment, a homopolymer of ethylene is produced.

[0112] In another embodiment, a homopolymer of 1-hexene is produced.

[0113] The cyclometallated catalyst system of the present invention canalso include one of more other transition metal compounds, such asconventional Ziegler catalysts, metallocene catalysts, constrainedgeometry catalysts, or heat-activated supported chromium oxide (e.g.,Phillips-type) catalysts.

[0114] The cyclometallated catalysts of formula (I) and formula (II)and/or cyclometallated catalyst systems are optionally used with aninorganic solid or organic polymer support. Suitable supports includesilica, alumina, magnesia, titania, clays, zeolites, polymeric supportssuch as polyethylene, polypropylene, polystyrene, functionalizedpolystyrene and the like. The supports can be pretreated thermally orchemically to improve catalyst productivity or product properties. Thecyclometallated catalysts, activators or cyclometallated catalysts canbe deposited on the support in any desired manner. For example, thecatalyst can be dissolved in a solvent, combined with a suitable supportand, optionally, dried. Alternatively, an incipient-wetness techniquecan be used. Moreover, the support can simply be introduced into thereactor separately from the catalyst.

[0115] As noted above, the cylometallated catalyst can be used in avariety of well-known olefin polymerization processes, including gas,high-pressure liquid, slurry, bulk, solution, or suspension-phasetechniques, and combinations of these. The liquid phase processcomprises the steps of contacting an olefin monomer with thecyclometallated catalyst system in a suitable polymerization solvent andreacting said monomer in the presence of said cyclometallated catalystsystem for a time and at a temperature and pressure sufficient toproduce a polyolefin. The pressures used typically range from about 10psi to about 15,000 psi. Polymerization temperatures range from about−100° C. to about 300° C. More preferably, the polymerizationtemperature ranges from about −80° C. to about 200° C. Most preferably,the polymerization temperature ranges from about from about −60° C. toabout 100° C.

[0116] The polymerization process of the present invention is highlyproductive, i.e., very small quantities of the catalysts are consumed inthe polymerization process. Such highly productive processes aredesirable, because the amount of catalysts or residues in the finalpolymer will be very small, thereby eliminating the need to separate orremove residual catalyst from the polymer product.

[0117] In one embodiment, the activity of the ethylene polymerizationprocess of this invention can be greater than 1700 g of polymer per mmolof catalyst per hour per atmosphere of ethylene, which corresponds to acatalyst turnover frequency (TOF) of greater than 6.1×10⁴ per hour peratmosphere of ethylene.

[0118] Preferably, the cyclometallated catalysts, activators andcyclometallated catalyst systems are prepared and stored under oxygen-and moisture-free conditions. For example, the preparative reactions areperformed with anhydrous solvent and under inert atmosphere, e.g., underhelium or nitrogen.

[0119] The following examples are set forth to illustrate the presentinvention, and are not meant to limit the scope of the invention. Thoseskilled in the art will recognize many variations that are within thespirit of the invention and scope of the claims.

EXAMPLES

[0120] All experiments were performed under a nitrogen atmosphere usingstandard Schlenk techniques and/or in a dry box available from M. Braun(Garching, Germany). ¹H and ¹³C NMR spectra were recorded on a BrukerAVANCE™ 600, 500 DRX, 400 or 300 FT-NMR spectrometer (ppm). ¹⁹F NMRspectra were recorded on the Bruker AVANCE™ 400. Mass spectra (EI andFAB) were obtained on a Finnigan MAT™ 95 mass spectrometer. Polymermelting points were determined using a Perkin Elmer DSC7™. Catalystactivities were measured as grams of polymer per millimole of catalystper hour per atmosphere. Methylaluminoxane (MAO, 10-15 wt % solution intoluene) was prepared according to U.S. Pat. No. 4,665,208 to Turner.

Example 1

[0121] Example 1 describes the synthesis of Intermediate 1:

[0122] Following the procedure described in Silva et al., Tetrahedron53: 11645 (1997), a mixture of 3,5-di-tert-butyl-2-methoxyacetophenone(2.000 g, 7.62 mmol) and potassium tert-butoxide (1.700 g, 15.24 mmol)in THF (30 ml) was stirred for 2 hr at room temperature under nitrogenatmosphere. To the resultant pale brown suspension was added a solutionof 1-N,N-dimethylamino-3-phenyl-3-oxo-1-propene (1.330 g, 7.62 mmol;prepared from acetophenone) in THF, and the resultant mixture wasstirred for 12 hr at room temperature to provide a dark red solution. A2 M solution of ammonium acetate in acetic acid (30 ml) was added to thesolution, THF was removed by distillation over 2 hr, and the resultantmixture was added to CH₂Cl₂ (100 ml). The organic layer was collected,washed with water to remove excess acetic acid, neutralized withsaturated sodium bicarbonate solution, and washed with brine. Theorganic layer was dried over anhydrous magnesium sulphate, and volatilesremoved in vacuo. Flash chromatography of the resultant red oil (silicagel; n-hexane:ethyl acetate (20:1) eluent) followed by solventevaporation in vacuo afforded Intermediate 1 as a yellow powder. Yield:1.96 g, 69%.

[0123] Intermediate 1: 1H (500 MHz, CDCl₃): δ 1.37 (s, 9H, 5-tBu), 1.45(s, 9H, 3-^(t)Bu), 3.38 (s, 3H, OMe), 7.40-7.44 (m, 2H, H⁶ and H¹⁵),7.49 (t, J=7.8 Hz, 2H, H¹⁴), 7.64 (d, J=2.6 Hz, 1H, H⁴), 7.69 and 7.74(two dd, J=1.2 Hz, J=6.5 Hz, 2H, H⁸ and H¹⁰), 7.78 (t, J=7.7 Hz, 1H,H⁹), 8.13 (d, J=8.0 Hz, 2H, H¹³).

Example 2

[0124] Example 2 describes the synthesis of Intermediate 2:

[0125] Using the procedure described by Dietrich-Buchecker et al.,Tetrahedron 46:503 (1990), a mixture of Intermediate 1 (1.670 g, 4.48mmol) and molten pyridinium chloride (10.347 g, 89.54 mmol) was stirredunder N₂ atmosphere at 230° C. for 12 hr. The resultant crude-yellowsolid was washed with cold n-pentane to afford Intermediate 2 as ayellow solid. Yield: 1.08 g, 67%.

[0126] Intermediate 2: ¹H NMR (500 MHz, CDCl₃): δ 1.38 (s, 9H,5-^(t)Bu), 1.52 (s, 9H, 3-^(t)Bu), 7.43 (d, J=2.4 Hz, 1H, H⁶), 7.48 (t,J=7.3 Hz, 1H, H¹⁵), 7.55 (t, J=7.5 Hz, 2H, H¹⁴), 7.62 (dd, J=2.4 Hz,J=3.8 Hz, 1H, H⁹), 7.71 (d, J=2.4 Hz, 1H, H⁴), 7.87-7.91 (m, 2H, H⁸ andH¹⁰), 7.97 (d, J=8.6 Hz, 2H, H¹³), 14.75 (s, 1H, OH). ¹³C NMR (126 MHz,CDCl₃): δ 29.62 (3-CMe₃), 31.64 (5-CMe₃), 34.36 and 35.35 (CMe₃), 118.18(C⁹), 118.26 and 138.33 (C⁸ and C¹⁰), 121.01 (C⁴), 126.26 (C⁶), 126.94(C¹³), 129.09 (C¹⁴), 129.43 (C¹⁵); 4° carbons: 118.03, 137.63,1 38.27,139.79, 154.41, 156.85, 159.03.

[0127] FAB-MS (+ve, m/z): 359 [M⁺].

Example 3

[0128] Example 3 describes the synthesis of Catalyst 1:

[0129] A solution of Intermediate 2 (0.400 g, 1.11 mmol) inpentane/diethyl ether (5:1) was slowly added to a stirred solution ofZr(CH₂Ph)₄ (0.507 g, 1.11 mmol) in pentane/diethyl ether (5:1) at −78°C. The resultant mixture was allowed to warm to room temperature andstirred for 12 hr during which a solution formed. The solution wasfiltered, concentrated to ca. 10 ml, and stored at −15° C. for 2-3 daysto provide orange crystalline solids. Recrystallization from pentaneafforded Catalyst 1 as large orange crystals. Yield: 0.53 g, 76%.

[0130] Catalyst 1: The X-ray crystal structure for Catalyst 1 (FIG. 4)shows that the benzyl groups are cis to each other. ¹H NMR (400 MHz,C₆D₆): δ 1.37 (s, 9H, 5-^(t)Bu), 1.60 (s, 9H, 3-^(t)Bu), 2.40 (d, J=9.3Hz, 2H, CH₂), 2.55 (d, J=9.3 Hz, 2H, CH₂), 6.67 (m, 2H,p-Ph), 6.85 (m,8H, o-Ph and m-Ph), 6.90 (t, J=8.0 Hz, 1H, H⁹), 7.07 (d, J=8.1 Hz, 1H,H¹⁰), 7.15 (fused with C₆D₆, 1H, H¹⁴), 7.18 (d, J=7.9 Hz, 1H, H⁸), 7.23(t, J=7.0 Hz, 1H, H¹⁵), 7.37 (d, J=7.9 Hz, 1H, H¹³), 7.39 (d, J=2.3 Hz,1H, H⁶), 7.63 (d, J=2.3 Hz, 1H, H⁴), 7.96 (d, J=7.0 Hz, 1H, H¹⁶). ¹³CNMR (126 MHz, C₆D₆): δ 30.71 (3-CMe₃), 32.19 (5-CMe₃), 34.90 and 35.89(CMe₃), 66.36 (J_(CH)=135.0 Hz, CH₂), 116.70 (C¹⁰), 123.46 (C⁸), 123.75(p-Ph), 123.82 (C¹³), 125.67 (C⁶), 126.85 (C⁴), 128.90 (C¹⁴), 129.20(C¹⁵), 129.67 and 130.81 (o-Ph and m-Ph), 135.41 (C¹⁶), 139.27 (i-Ph),140.10 (C⁹), 191.65 (C¹⁷); 4° carbons: 126.89, 136.95, 142.02, 143.99,156.09, 159.18, 165.07. Anal. Calcd. (%) For C₃₉H₄₁NOZr (630.98): C,74.24; H, 6.55; N, 2.22. Found: C, 65.37; H, 6.10; N, 2.47.

Example 4

[0131] Example 4 describes the synthesis of Catalyst 2:

[0132] A solution of Intermediate 2 (0.270 g, 0.75 mmol) in toluene/THF(5:1) was slowly added to a to a stirred solution of[Zr(CH₂Ph)₂Cl₂(OEt₂)(dioxane)_(0.5)] (0.350 g, 0.75 mmol) in toluene/THF(5:1) at −78° C. The reaction mixture was allowed to warm up to roomtemperature and stirred for 12 hr, during which time a yellow solutionformed. The solution was filtered, concentrated to ca. 10 ml and storedat −78° C. for 2-3 days. The resultant yellow solid was isolated,recrystallized from toluene, and isolated and dried in vacuo to affordCatalyst 2 with one equivalent of toluene as bright yellow crystals.Yield: 0.36g,70%.

[0133] Catalyst 2: The X-ray crystal structure for Catalyst 2 (FIG. 5),shows that the chloro groups are cis to each other. ¹H NMR (500 MHz,CDCl₃): δ 1.36 (s, 9H, 5-^(t)Bu), 1.51 (s, 9H, 3-^(t)Bu), 1.66 (br, 4H,thf), 2.35 (s, 3H, PhMe), 3.75 (br, 4H, thf), 7.14-7.24 (m, SH, PhMe),7.27-7.32 (m, 2H, H¹⁴ and H¹⁵), 7.50 (d, J=2.3 Hz, 1H, H⁶), 7.54 (d,J=2.3 Hz, 1H, H⁴), 7.71 (d, J=7.4 Hz, 1H, H 16), 7.80-7.82 (two d, J=7.8and 8.2 Hz, 2H, H⁸ and H¹⁰), 7.96 (t, J=8.0 Hz, 1H, H⁹), 8.25 (d, J=6.6Hz, 1H, H¹³). ¹³C NMR (126 MHz, CDCl₃): δ 21.48 (PhMe), 25.20 (thf),30.16 (3-CMe₃), 31.62 (5-CMe₃), 34.59 and 35.33 (CMe₃), 73.76 (thf),116.80 and 122.98 (C⁸ and C¹⁰), 123.06 (C¹³), 124.42 (C⁴), 125.32,128.25, 129.06 and 137.92 (PhMe), 127.16 (C₆), 128.85 (C¹⁴), 129.67(C¹⁵), 137.04 (C¹⁶), 140.73 (C⁹), 187.75 (C¹⁷); 4° carbons: 124.48,137.44, 142.69, 142.88, 155.21, 158.01, 164.05. Anal. Calcd. (%) ForC₃₆H₄₃Cl₂NO₂Zr (683.87): C, 63.23; H, 6.34; N, 2.05. Found: C, 63.31; H,6.22; N, 2.08.

Example 5

[0134] Example 5 describes the synthesis of Intermediate 3:

[0135] Following the procedure described above for preparingIntermediate 1, a mixture of 3,5-di-tert-butyl-2-methoxyacetophenone(1.687 g, 6.43 mmol) and potassium tert-butoxide (1.460 g, 13.00 mmol)in THF (30 ml) was stirred for 2 hr at room temperature under nitrogenatmosphere, and a solution of1-N,N-dimethylamino-3-(3,5-bis(trifluoromethylphenyl))-3-oxo-1-propene(2.000 g, 6.43 mmol) in THF was added. The resultant mixture was stirredfor 12 hr at room temperature during which time a dark red solutionformed. A 2M solution of ammonium acetate in acetic acid (30 ml) wasadded to the solution, THF was removed by distillation over 2 hr, andthe resultant mixture was added to CH₂Cl₂ (100 ml) The organic layer wascollected, washed with water to remove excess acetic acid, neutralizedwith saturated sodium bicarbonate solution, and washed with brine. Theorganic layer was dried over anhydrous magnesium sulphate, and volatilesremoved in vacuo. Reaction of the resultant red oil (1.211 g) withmolten pyridinium chloride (4.125 g, 35.70 mmol) under N₂ atmosphere at230° C. for 12 hr as described above in Example 1 yielded a crude yellowsolid. The crude solid was then washed with cold n-pentane to affordIntermediate 3 as a yellow solid. Yield: 0.89 g, 70%.

[0136] Intermediate 3: ¹H NMR (500 MHz, CDCl₃): δ 1.38 (s, 9H,5-^(t)Bu), 1.50 (s, 9H, 3-^(t)Bu), 7.46 (d, J=2.4 Hz, 1H, H⁶), 7.67-7.69(m, 2H, H⁴ and H⁹), 7.95-8.00 (m, 3H, H⁸, H¹⁰ and H¹⁵), 8.39 (s, 2H,H¹³), 13.92 (s, 1H, OH). ¹³C NMR (126 MHz, CDCl₃): δ 29.58 (3-CMe₃),31.61 (5-CMe₃), 31.74 and 34.41 (CMe₃), 118.49 (C⁹), 120.17 and 138.89(C⁸ and C¹⁰), 121.26 (C⁴), 122.94 (m, C¹⁵), 126.86 (C⁶), 127.06 (m,C¹³), 132.58 (q, J_(CF)=33.6 Hz, CF₃); 4° carbons: 117.93, 137.94,140.41, 140.52, 151.55, 156.38, 159.88. ¹⁹F NMR (376 MHz, CDCl₃): δ−63.39. El-MS (+ve, m/z): 495 [M⁺].

Example 6

[0137] Example 6 describes the synthesis of Catalyst 3:

[0138] A solution of Intermediate 3 (0.200 g, 0.40 mmol) inpentane/diethyl ether (5:1) was slowly added to a stirred solution ofZr(CH₂Ph)₄ (0.184 g, 0.40 mmol) in pentane/diethyl ether (5:1) at −78°C. The reaction mixture was allowed to warm up to room temperature andstirred for 12 hr during which time a solution formed. The solution wasfiltered, concentrated to ca. 10 ml and stored at −15° C. for 2-3 daysto provide a red crystalline solid. Recrystallization from pentaneafforded Catalyst 3 as large red crystals. Yield: 0.23 g, 75%.

[0139] Catalyst 3: The X-ray crystal structure for Catalyst 3 (FIG. 6)shows that the benzyl groups are cis to each other. ¹H NMR (400 MHz,C₆D₆): δ 1.36 (s, 9H, 5-^(t)Bu), 1.72 (s, 9H, 3-^(t)Bu), 3.09 (dq, J=9.6Hz, ^(1h)J_(HF)=3.3 Hz, 2H, H²⁰′ and H²¹′), 3.26 (d, J=9.4 Hz, 2H, H²⁰and H²¹), 6.18 (t, J=7.3 Hz, 2H, p-Ph), 6.25 (t, J=7.7 Hz, 4H, m-Ph),6.54 (d, J=7.4 Hz, 4H, o-Ph), 6.57 (d, J=7.9 Hz, 1H, H¹⁰), 6.77 (t,J=8.0 Hz, 1H, H⁹), 7.25 (d, J=8.0 Hz, 1H, H⁸), 7.40 (d, J=2.3 Hz, 1H, H⁶), 7.60 (s, 1H, H¹³ ), 7.69 (d, J=2.4 Hz, 1H, H⁴), 7.81 (s, 1H, H¹⁵).¹³C NMR (126 MHz, C₆D₆): δ 31.28 (3-CMe₃), 32.12 (5-CMe₃), 34.97 and36.06 (CMe₃), 70.50 (q, ^(2h)J_(CF)=5.9 Hz (J_(CH)=133.3 Hz), C²⁰ andC²¹), 118.10 (C¹⁰), 127.64 (C⁴), 122.08 (br, C¹⁵), 123.18 (br, C¹³),123.81 (p-Ph), 124.44 (C⁸), 125.35 (C⁶), 129.10 (o-Ph), 129.94 (m-Ph),130.78 and 138.49 (q, J_(CF)=31.1 Hz, C¹⁸ and C¹⁹), 136.92 (i-Ph),139.25 (C⁹), 189.87 (C¹⁷); 40 carbons: 126.68, 138.08, 142.78, 145.09,155.26, 159.33, 161.55. ¹⁹F NMR (376 MHz, C₆D₆): δ −58.09 (F⁹), −62.56(F¹⁸). El-MS (+ve, m/z): 765 [M+]. Anal. Calcd. (%) For C₄₁H₃₉F₆NOZr(766.98): C, 64.21; H, 5.13; N, 1.83. Found: C, 63.99; H, 5.57; N,1.89.]

[0140] The NMR data indicate C—F . . . H—C interactions between the —CF₃group (R¹¹) and the benzyl groups. The NMR results suggest thatintramolecular attractive weak interaction may also occur duringpolymerization between the —CF₃ group and the polymer chain (e.g. C—F. .. H—C). Such weak non-covalent interactions could be advantageously usedto affect catalyst reactivity, stabilize reactive intermediates andcontrol polymer properties (e.g., stereoselectivity). For example, thesetypes of intramolecular weak non-covalent attractive interactions cansuppress H-transfer and chain termination processes duringpolymerization and may also afford highly stereoselective polymers.

Example 7

[0141] Example 7 describes the synthesis of Catalyst 4:

[0142] A solution of Intermediate 3 (0.214 g, 0.43 mmol) inpentane/diethyl ether (5:1) was slowly added to a stirred solution ofTi(CH₂Ph)₄ (0.178 g, 0.43 mmol) in pentane/diethyl ether (5:1) at −78°C. The resultant mixture was allowed to warm to room temperature andstirred for 12 hr during which time a solution formed. The solution wasfiltered and volatiles removed in vacuo. The resultant crude dark redcrystalline solid was recrystallized from pentane to afford Catalyst 4as dark red crystals. Yield: 0.18 g, 57%.

[0143] Catalyst 4: ¹H NMR (500 MHz, C₆D₆): δ 1.34 (s, 9H, 5-^(t)Bu),1.77 (s, 9H, 3-^(t)Bu), ), 4.00 (dq, J=8.4 Hz, ^(1h)J_(HF)=1.2 Hz, 2H,H²⁰′ and H²¹′), 4.04 (d, J=8.3 Hz, 2H, H²⁰ and H²¹), 6.25 (t, J=7.2 Hz,2H, p-Ph), 6.32 (t, J=7.1 Hz, 4H, m-Ph), 6.42 (d, J=8.3 Hz, 1H, H¹⁰),6.44 (d, J=7.3 Hz, 4H, o-Ph), 6.66 (t, J=8.0 Hz, 1H, H⁹), 7.21 (d, J=8.0Hz, 1H, H⁸), 7.40 (d, J=2.1 Hz, 1H, H⁶), 7.60 (s, 1H, H¹³), 7.70 (d,J=2.3 Hz, 1H, H⁴), 8.12 (s, 1H, H¹⁵). ¹³C NMR (126 MHz, C₆D₆): δ 31.08(3-CMe₃), 31.73 (5-CMe₃), 34.70 and 35.71 (CMe₃), 96.19 (q,^(2h)J_(CF)=5.3 Hz (J_(CH)=138.9 Hz), C²⁰ and C²¹), 116.58 (C¹⁰), 122.84(br, C¹³), 123.19 (br, C¹⁵), 123.40 (C⁸), 124.07 (p-Ph), 124.38 (C⁶),127.48 (C⁴), 127.57 (m-Ph), 131.13 and 137.23 (q, J_(CF)=32.5 and 30.2Hz respectively, C¹⁸ and C¹⁹), 130.51 (o-Ph), 137.57 (i-Ph), 139.28(C⁹), 193.37 (C¹⁷); 4° carbons: 127.29, 136.99, 143.08, 144.85, 156.83,156.89, 161.35. ¹⁹F NMR (376 MHz, C₆D₆): δ −56.45 (F⁹), −62.60 (F¹⁸).Anal. Calcd. (%) For C₄₁H₃₉F₆NOTi (723.66): C, 68.05; H, 5.43; N, 1.93.Found: C, 68.08; H, 5.58; N, 2.09.]

[0144] The NMR data indicate C—F. . . H—C interactions between the —CF₃group (R¹¹) and the benzyl groups. The NMR results suggest thatintramolecular attractive weak interaction may also occur duringpolymerization between the —CF₃ group and the polymer chain (e.g. C—F .. . H—C). Such weak non-covalent interactions could be advantageouslyused to affect catalyst reactivity, stabilize reactive intermediates andcontrol polymer properties (e.g., stereoselectivity). For example, thesetypes of intramolecular weak non-covalent attractive interactions cansuppress H-transfer and chain termination processes duringpolymerization and may also afford highly stereoselective polymers.

Example 8

[0145] Example 8 describes the synthesis of Intermediate 4:

[0146] Following the procedure described above for preparingIntermediate 1, a mixture of 3,5-di-tert-butyl-2-methoxyacetophenone(2.500 g, 9.53 mmol) and potassium tert-butoxide (2.200 g, 19.06 mmol)in THF (30 ml) was stirred for 2 hr at room temperature under nitrogenatmosphere, and a solution of1-NN-dimethylamino-3-(3′-trifluoromethylphenyl)-3-oxo-1-propene (2.315g, 9.53 mmol) in THF (30 ml) was added. The resultant mixture wasstirred for 12 hr during which time a dark red solution formed. A 2Msolution of ammonium acetate in acetic acid (30 ml) was added to thesolution, THF was removed by distillation over 2 hr, and the resultantmixture was added to CH₂Cl₂ (100 ml). The organic layer was collected,washed with water to remove excess acetic acid, neutralized withsaturated sodium bicarbonate solution, and washed with brine. Theorganic layer was dried over anhydrous magnesium sulphate, and volatilesremoved in vacuo. The resultant red oil (2.993 g) was then reacted withmolten pyridinium chloride (11.760 g, 102 mmol ) under N₂ atmosphere at230° C. for 12 hr as described above in Example 1. The resultant crudeyellow solid was washed with cold n-pentane to afford Intermediate 4 asa yellow solid. Yield: 2.35 g, 81%.

[0147] Intermediate 4: ¹H NMR (500 MHz, CDCl₃): δ 1.38 (s, 9H,5-^(t)Bu), 1.50 (s, 9H, 3-^(t)Bu), 7.44 (d, J=2.4 Hz, 1H, H⁶), 7.64 (dd,J=2.5 Hz, J=3.7 Hz, 1H, H⁹), 7.67-7.69 (m, 2H, H⁴ and H¹⁶), 7.73 (d,J=7.8 Hz, 1H, H¹⁵), 7.91-7.95 (m, 2H, H⁸ and H¹⁰), 8.16-8.18 (s and d,2H, H¹³ and H¹⁷), 14.36 (s, 1H, OH). ¹³C NMR (126 MHz, CDCl₃): δ 29.62(3-CMe₃), 31.62 (5-CMe₃), 34.39 and 35.37 (CMe₃), 118.32 (C⁹), 119.18and 138.61 (C⁸ and C¹⁰), 121.14 (C⁴), 123.79 and 126.02 (m, C¹³ andC¹⁵), 126.55 (C⁶), 129.76 and 130.33 (C¹⁶ and C¹⁷), 131.47 (q,J_(CF)=32.3 Hz, CF₃); 4° carbons: 117.97, 137.76, 139.15, 140.10,153.01, 156.63, 159.42. ¹⁹F NMR (376 MHz, CDCl₃): δ −63.15. EI-MS (+ve,m/z): 427 [M⁺].

Example 9

[0148] Exameple 9 describes the synthesis of Catalyst 5:

[0149] A solution of Intermediate 4 (0.251 g, 0.59 mmol) inpentane/diethyl ether (5:1) was slowly added to a stirred solution ofZr(CH₂Ph)₄ (0.270 g, 0.59 mmol) in pentane/diethyl ether (5:1) at −78°C. The reaction mixture was allowed to warm up to room temperature andstirred for 12 hr during which time a solution formed. The solution wasfiltered, concentrated to ca. 10 ml and stored at −15° C. for 2-3 daysto provide a crude orange-red crystalline solid. Recrystallization frompentane afforded Catalyst 5 as large orange-red crystals. Yield: 0.23 g,60%.

[0150] Catalyst 5: The X-ray crystal structure for Catalyst 5 (FIG. 7)shows that the benzyl groups are cis to each other. ¹H NMR (500 MHz,C₆D₆): δ 1.36 (s, 9H, 5-^(t)Bu), 1.58 (s, 9H, 3-^(t)Bu), 2.27 (d, J=9.3Hz, 2H, CH₂), 2.49 (d, J=9.3 Hz, 2H, CH₂), 6.64 (t, J=7.3 Hz, 2H, p-Ph),6.71 (d, J=7.2, 4H, o-Ph), 6.80 (m, 5H, m-Ph and H¹⁰), 6.86 (t, =7.9 Hz,1H, H⁹), 7.20 (d, J=7.4 Hz, 1H, H⁸), 7.39 (d, J=2.3 Hz, 1H, H⁶), 7.41(d, J=7.3 Hz, 1H, H¹⁵), 7.63 (d, J=2.4 Hz, 1H, H⁴), 7.70 (s, 1H, H¹³),7.79 (d, J=7.3 Hz, 1H, H¹⁶). ¹³C NMR (126 MHz, C₆D₆): δ 30.64 (3-CMe₃),32.13 (5-CMe₃), 34.93 and 35.85 (CMe₃), 66.33 (J_(CH)=135.0 Hz, CH₂),117.22 (C¹⁰), 120.04 (m, C¹³), 124.10 (p-Ph and C⁸), 124.93 (m, C¹⁵),125.71 (C⁶), 127.12 (C⁴), 129.55 (o-Ph), 130.04 (q, JCF =31.7 Hz, CF₃),131.13 (m-Ph), 136.11 (C¹⁶), 140.35 (C⁹), 138.61 (i-Ph), 194.65 (C¹⁷);4° carbons: 126.89, 137.01, 142.47, 144.42, 155.75, 159.25, 163.53. ¹⁹FNMR (376 MHz, C₆D₆): δ −2.27. Anal. Calcd. (%) For C₄₀H₄₀F₃NOZr(698.98): C, 68.73; H, 5.77; N, 2.00. Found: C, 68.21; H, 5.68; N, 2.02.

Example 10

[0151] Example 10 describes the synthesis of Intermediate 5:

[0152] Following the procedure described above for preparingIntermediate 1, a mixture of 3,5-di-tert-butyl-2-methoxyacetophenone(2.99 g, 11.40 mmol) and potassium tert-butoxide (2.56 g, 22.80 mmol) inTHF was stirred for 2 hr at room temperature under nitrogen atmosphere,and a solution of1-N,N-dimethylamino-3-(3′-trifluoromethylphenyl)-3-oxo-1-propene (2.94g, 11.30 mmol ) in THF (30 ml) was added. The resultant mixture wasstirred for 12 hr at room temperature during which time a dark redsolution formed. A 2M solution of ammonium acetate in acetic acid (30ml) was added to the solution, THF was removed by distillation over 2hr, and the resultant mixture was added to CH₂Cl₂ (100 ml). The organiclayer was collected, washed with water to remove excess acetic acid,neutralized with saturated sodium bicarbonate solution, and washed withbrine. The organic layer was dried over anhydrous magnesium sulphate,and volatiles removed in vacuo. The resultant red oil (2.635 g) wasreacted with molten pyridinium chloride (6.63 g, 57.40 mmol ) under N₂atmosphere at 230° C. for 12 hr as described above in Example 1. Theresultant crude yellow solid was washed with cold n-pentane to affordIntermediate 4 as a yellow solid. Yield: 1.74 g, 68%.

[0153] Intermediate 5: ¹H NMR (500 MHz, CDCl₃): δ 1.37 (s, 9H,5-^(t)Bu), 1.50 (s, 9H, 3-^(t)Bu), 7.43 (d, J=8.0 Hz, 1H, H¹⁵), 7.45 (d,J=2.4 Hz, 1H, H 6), 7.63 (m, 1H, H⁹), 7.68 (d, J=2.4 Hz, 1H, H⁴), 7.86(d, J=9.3 Hz, 1H, H¹⁷), 7.95 (m, 2H, H⁸ and H¹⁰), 7.97 (s, 1H, H¹³),14.06 (s, 1H, OH). ¹³C NMR (126 MHz, CDCl₃): δ 29.76 (3-CMe₃), 31.72(5-CMe₃), 34.55 and 35.53 (CMe₃), 113.70 (dq, ²JcF =24.8 Hz, ³J_(CF)=3.5Hz, C¹⁵), 117.52 (d, ²J_(CF)=22.7 Hz, C¹⁷), 118.57 (C⁹), 119.71 (m, ³JCF=3.7 Hz, C¹³), 120.05 and 138.89 (C⁸ and C¹⁰), 121.36 (C⁴), 126.90 (C⁶),133.50 (m, CF₃), 163.23 (d, ¹J_(CF)=250.0 Hz, C¹⁶); 4° carbons: 6118.07,138.03, 140.45, 141.90, 141.96, 151.97, 156.63, 159.83. ¹⁹F NMR (376MHz, CDCl₃): δ −63.29 (CF₃), −109.75 (F¹⁶). FAB-MS (+ve, m/z): 445 [M⁺].

Example 11

[0154] Example 11 describes the synthesis of Catalyst 6:

[0155] A solution of Intermediate 5 (0.200 g, 0.45 mmol) in toluene/THF(5:1) was slowly added to a stirred solution of[Zr(CH₂Ph)₂Cl₂(OEt₂)(dioxane)_(0.5)] (0.208 g, 0.45 rnmol) intoluene/THF (5:1) at −78° C. The reaction mixture was allowed to warm toroom temperature and stirred for 12 hr during which time a yellowsolution formed. The solution was filtered, concentrated to ca. 10 mland stored at −78° C. for 2-3 days to provide a crude yellow solid. Thesolid was isolated and recrystallized from toluene to afford Catalyst 6as orange crystals. Yield: 0.25 g, 78%.

[0156] Catalyst 6: ¹H NMR (600 MHz, C₆D₆): δ 0.83 (br, 4H, thf), 1.32(s, 9H, 5-^(t)Bu), 1.68 (s, 9H, 3-^(t)Bu), 3.46 (br, 4H, thf), 6.84 (d,J=7.7 Hz, 1H, H¹⁰), 6.99 (t, J=8.0 Hz, 1H, H⁹), 7.19 (d, ³J_(HF)=4.0 Hz,1H, H¹⁵), 7.34 (d, J=8.0 Hz, 1H, H⁸), 7.48 (d, J=2.3 Hz, 1H, H⁶), 7.56(s, 1H, H¹³), 7.68 (d, J=2.3 Hz, 1H, H⁴). ¹³C NMR (151 MHz, C₆D₆): δ25.33 (thf), 30.68 (3-CMe₃), 32.02 (5-CMe₃), 35.06 and 36.05 (CMe₃),73.87 (thf), 113.55 (dq, ²J_(CF)=31.9 Hz, ³J_(CF)=3.6 Hz, C¹⁵), 117.15(q,3J_(CF)=3.3 Hz, C¹³), 118.36 (C¹⁰), 124.22 (C⁵), 125.06 (C⁶), 127.98(C⁴), 133.08 (m, CF₃), 141.17 (C⁹), 147.68 (d, JCF =21.4 Hz, C¹⁶); 4°carbons, 138.71, 144.07, 155.45, 158.87, 162.52, 166.33, 167.89, 170.04,170.46. ¹⁹F NMR (376 MHz, C₆D₆): −62.37 (CF₃), −84.01 (F¹⁶). Anal.Calcd. (%) For C₃₀H₃₃F₄NO₂ZrCl₂ (679.126): C, 53.17; H, 4.91; N, 2.07.Found: C, 49.43; H, 4.89; N, 2.03.

Example 12

[0157] Example 12 describes the reaction of Catalyst 3 with theactivator tris(pentafluorophenyl)boron, B(C₆F₅)₃.

[0158] Catalyst 3 was reacted with 1 equivalent of B(C₆F₅)₃ in CD₂Cl₂and d₈-THF in an NMR tube. As shown in FIG. 8, the broad upfield ¹Hdoublet peak for one of the methylene protons and the downfield ¹⁹Fresonance for the proximal CF₃ group are both partially sharpened upondecoupling of the ¹⁹F and ¹H nuclei respectively. It is noted that the¹³C{¹H} NMR spectrum (400 MHz) contains a slightly broad but resolvedquartet signal at 76.9 ppm (^(2h)J_(CF)=4 Hz) for the ZrCH₂ group. TheNMR spectrum indicated formation of a η²-benzyl cation that ispresumably stabilized by the d₈-THF ligand.

Example 13

[0159] Example 13 describes the results of ethylene polymerization usingCatalyst 1 as catalyst and MAO as activator.

[0160] The ethylene polymerization was performed under 1 atm ethyleneoverpressure in toluene in a 100 mL glass reactor equipped with amagnetic stir bar. Catalyst 1 (5.8 mg, 9.19 μmol ) and toluene (20 mL)were added to the reactor and stirred to form a solution. The reactorwas submerged in a liquid bath at 23° C. for 30 minutes, and a toluenesolution of methylaluminoxane (MAO) (9.19 mmol, 1000 equivalents) wasadded. Polymerization was initiated by purging with ethylene gas for 5minutes, and the reactor was maintained under 1 atmosphere (atm) ofethylene for 10 minutes at 23° C. The ethylene gas feed was stopped, andthe polymerization was terminated by addition of HCl-acidified methanol(40 mL). The resultant solid polymer was collected by filtration, washedwith acidified methanol and dried in vacuum at 60° C. for 12 h to afford0.013 g of polymer. Melting point: 128° C. The calculated activity ofCatalyst 1 was 11.7 g mmol⁻¹ h⁻¹ atm⁻¹.

Example 14

[0161] Ethylene polymerization was performed as described above inExample 13 using Catalyst 3 (5.3 mg, 6.91 μmol) and MAO (6.91 mmol; 1000equivalents) for 10 min at 23° C. to afford 0.130 g of polymer. Meltingpoint: 131° C. The calculated activity of Catalyst 3 was 113 g mmol⁻¹h⁻¹ atm⁻¹.

Example 15

[0162] Ethylene polymerization was performed as described above inExample 13 using Catalyst 3 (7.2 mg, 9.39 μmol) and MAO (9.39 mmol; 1000equivalents) for 10 min at −3° C. to afford 0.403 g of polymer. Meltingpoint: 130° C. The calculated activity of Catalyst 3 was 258 g mmol⁻¹h⁻¹ atm⁻¹.

Example 16

[0163] Ethylene polymerization was performed as described above inExample 13 using Catalyst 3 (5.5 mg, 7.17 μmol) and MAO (7.17 mmol; 1000equivalents) for 10 min at 50° C. to afford 0.130 g of polymer. Meltingpoint: 132° C. The calculated activity of Catalyst 3 was 109 g mmol⁻¹h⁻¹ atm⁻¹.

Example 17

[0164] Ethylene polymerization was performed as described above inExample 13 using Catalyst 3 (5.3 mg, 6.91 μmol) and MAO (13.8 mmol; 2000equivalents) for 10 min at 23° C. to afford 0.914 g of polymer. Meltingpoint: 131° C. The calculated activity of Catalyst 3 was 793 g mmol⁻¹h⁻¹ atm⁻.

Example 18

[0165] Ethylene polymerization was performed as described above inExample 13 using Catalyst 5 (4.7 mg, 6.72 μmol) and MAO (6.72 mmol; 1000equivalents) for 10 min at 23° C. to afford 0.006 g of polymer. Thecalculated activity of Catalyst 5 was 4 g mmol⁻¹ h⁻¹ atm⁻¹.

Example 19

[0166] Ethylene polymerization was performed as described above inExample 13 using Catalyst 6 (7.1 mg, 10.31 μmol) and MAO (10.31 mmol;1000 equivalents) for 10 min at 23° C. to afford 1.022 g of polymer.Melting point: 125° C. The calculated activity of Catalyst 7 was 595 gmmol⁻¹ h⁻¹ atm⁻¹.

Example 20

[0167] Ethylene polymerization was performed as described above inExample 13 using Catalyst 4 (5.2 mg, 7.18 μmol) and MAO (7.18 mmol; 1000equivalents) for 2 min at 24° C. to afford 0.396 g of polymer. Meltingpoint: 134° C. The calculated activity of Catalyst 4 was 1654 g mmol⁻¹h⁻¹ atm⁻¹.

Example 21

[0168] Ethylene polymerization was performed as described above inExample 13 using Catalyst 4 (5.4 mg, 7.46 μmol) and MAO (7.46 mmol; 1000equivalents) for 2 min at 0° C. to afford 0.434 g of polymer. Meltingpoint: 136° C. The calculated activity of Catalyst 4 was 1744 g mmol⁻¹h⁻¹ atm⁻¹.

Example 22

[0169] Ethylene polymerization was performed as described above inExample 13 using Catalyst 4 (5.0 mg, 6.91 μmol) and MAO (6.91 mmol; 1000equivalents) for 2 min at 50° C. to afford 0.209 g of polymer. Meltingpoint: 133° C. The calculated activity of Catalyst 4 was 907 g mmol⁻¹h⁻¹ atm⁻¹.

Example 23

[0170] Example 23 describes the results of 1-hexene polymerization usinga catalyst prepared from Catalyst 1 and MAO.

[0171] Polymerization of 1-hexene was performed at 1 atm. pressure intoluene in a 100 mL glass reactor equipped with a magnetic stir bar.Catalyst 1 (5.0 mg, 7.92 μmol) and toluene (20 mL) were added to thereactor and stirred to form a solution. A toluene solution ofmethylaluminoxane (MAO) (7.92 mmol; 1000 equivalents) was added to thereactor and the contents stirred. The reactor was submerged in a liquidbath at 23° C. for 10 minutes, neat 1-hexene (5 mL) was added to thereactor, and the polymerization was performed for 5 hr Thepolymerization was then terminated by addition of HCl-acidified methanol(40 mL). The resultant polymer was extracted with CH₂Cl₂, precipitatedwith methanol, and dried in vacuum for 12 hr to afford 0.246 g ofpolymer. The calculated activity of Catalyst 1 was 6.2 g mmol⁻¹ h⁻¹.

Example 24

[0172] 1-Hexene polymerization was perfonned as described above inExample 23 using Catalyst 3 (5.5 mg, 7.17 μmol) and MAO (7.92 mmol; 1000equivalents) for 5 hr at 23° C. to afford 0.387 g of polymer. Thecalculated activity of Catalyst 3 was 10.8 g mmol⁻¹ h⁻¹.

Example 25

[0173] 1-Hexene polymerization was performed as described above inExample 23 using Catalyst 3 (6.7 mg, 8.74 μmol) and MAO (8.74 mmol; 1000equivalents) for 5 hr at 0° C. to afford 0.119 g of polymer. Thecalculated activity of Catalyst 3 was 2.7 g mmol⁻¹ h⁻¹.

[0174] As is apparent from the previous general description and thespecific embodiments, while forms of the invention have been illustratedand described, various modifications can be made without departing fromthe scope and spirit of the invention. Accordingly, it is not intendedthat the invention be limited thereby.

[0175] A number of references have been cited and the entire disclosuresof which are incorporated herein by reference.

What is claimed is:
 1. A catalyst of formula:

wherein: R¹-R⁷ are each independently —H, -halo, —NO₂, —CN,-(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl, or-heteroaryl, each of which may be unsubstituted or substituted with oneor more -R⁸ groups; or two R¹-R⁷ may be joined to form cyclic group; R⁸is -halo, -(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —NO₂, —CN,—Si((C₁-C₃₀)hydrocarbyl)₃, —N((C₁-C₃₀)hydrocarbyl)₂,-(C₁-C₃₀)heterohydrocarbyl, -aryl, or -heteroaryl; T is —CR⁹R¹⁰— whereinR⁹and R¹⁰ are defined as for R¹ above; E is a Group 16 element; M is ametal selected from the group consisting of metallic Group 3-Group 10elements and the Lanthanide series elements; m is the oxidation state ofthe M; X is R¹ excluding —H, wherein X is bonded to M; Y is neutralligand datively bound to M; and n is an integer ranging from 0 to
 5. 2.The catalyst of claim 1, wherein M is titanium, zirconium or hafnium. 3.The catalyst of claim 2, wherein X is halide, unsubstituted-(C₁-C₃₀)hydrocarbyl or substituted -(C₁-C₃₀)hydrocarbyl.
 4. Thecatalyst of claim 3, wherein X is benzyl.
 5. The catalyst of claim 2,wherein E is —O—.
 6. An olefin polymerization catalyst system preparedfrom the catalyst of claim 1 and an activator.
 7. The olefinpolymerization catalyst of claim 6, wherein the activator is selectedfrom the group consisting of trimethylaluminum, triethylaluminum,tri-isobutylaluminum, tri-n-octylaluminum, methylaluminum dichloride,ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminumchloride, aluminoxanes, tetrakis(pentafluorophenyl)borate,dimethylphenylammonium tetra(pentafluorophenyl)borate, trityltetra(pentafluorophenyl)borate, tris(pentafluorophenyl)boron,tris(pentabromophenyl)boron, and mixtures thereof.
 8. A method forpolymerizing an olefin comprising contacting an olefin with the olefinpolymerization catalyst system of claim
 7. 9. The method of claim 8,wherein the olefin is ethylene, propylene, 1-butene, 2-pentene,1-hexene, 1-octene, styrene, 1,3-butadiene, norbornene, each of whichmay be substituted or unsubstituted, or mixtures thereof.
 10. The methodof claim 9, wherein the olefin is ethylene or 1-hexene.
 11. The methodof claim 8, wherein at least one of R¹-R⁷ and R⁹-R¹⁰ is selected fromthe group consisting of —C(halide)₃, CH(halide)₂ and —CH₂(halide).
 12. Acatalyst of formula:

wherein R¹-R¹¹ each independently —H, -halo, —NO₂, —CN,-(C₁-C₃₀)hydrocarbyl, —O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl,-heteroaryl, each of which may be unsubstituted or substituted with oneor more -R¹² groups; or two R¹-R⁷ may be joined to form a cyclic group;each R¹² is independently -halo, —NO₂, —CN, —(C₁-C₃₀)hydrocarbyl,—O(C₁-C₃₀)hydrocarbyl, —N((C₁-C₃₀)hydrocarbyl)₂,—Si((C₁-C₃₀)hydrocarbyl)₃, -(C₁-C₃₀)heterohydrocarbyl, -aryl, or-heteroaryl; E is a Group 16 element; M is a metal selected from thegroup consisting of metallic Group 3—Group 10 elements and theLanthanide series elements; m is the oxidation state of M; X is R¹excluding —H, wherein X is bonded to M; Y is neutral ligand dativelybound to M; and n is an integer ranging from 0 to
 5. 13. The catalyst ofclaim 12, wherein M is titanium, zirconium or haffiium.
 14. The catalystof claim 13, wherein M is Ti or Zr; E is —O—; m is 4; n is 0 or 1; and Xis halo, -(C₁-C₃₀)hydrocarbyl or benzyl.
 15. The catalyst of claim 13,wherein R¹¹ is —CF₃.
 16. The catalyst of claim 14, wherein M is Zr; R¹and R³ are —C(CH₃)₃; R² and R⁴-R¹¹ are —H; X is —CH₂(C₆H₅); and n is 0.17. The catalyst of claim 14, wherein M is Zr; R¹ and R³ are —C(CH₃)₃;R² and R⁴-R¹¹ are —H; X is —Cl; n is 1; and Y is -tetrahydrofuran. 18.The catalyst of claim 14, wherein M is Zr; R¹ and R³ are —C(CH₃)₃; R⁹and R¹¹ are —CF₃; R², R⁴-R⁸ and R¹⁰ are —H; X is —CH₂(C₆H₅); and n is 0.19. The catalyst of claim 14, wherein M is Ti; R¹ and R³ are —C(CH₃)₃;R⁹ and R¹¹ are —CF₃; R², R⁴-R⁸ and R¹⁰ are -H; X is —CH₂(C₆H₅); and n is0.
 20. The catalyst of claim 14, wherein M is Zr; R¹ and R are —C(CH₃)₃;R⁹ is —CF₃; R², R⁴-R⁸ and R¹⁰-R¹¹ are —H; X is —CH₂(C₆H₅); and n is 0.21. The catalyst of claim 14, wherein M is Zr; R¹ and R³ are —C(CH₃)₃;R⁹ is —CF₃; R¹¹ is —F; R², R⁴-R⁸ and R¹⁰ are —H; X is —Cl; n is 1; and Yis tetrahydrofuran.
 22. An olefin polymerization catalyst systemprepared from the catalyst of claim 12 and an activator.
 23. The olefinpolymerization catalyst system of claim 22, wherein the activator isselected from the group consisting of trimethylaluminum,triethylaluminum, tri-isobutylaluminum, tri-n-octylaluminum,methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminumchloride, diethylaluminum chloride, aluminoxanes,tetrakis(pentafluorophenyl)borate, dimethylphenylammoniumtetra(pentafluorophenyl)borate, trityl tetra(pentafluorophenyl)borate,tris(pentafluorophenyl)boron, tris(pentabromophenyl)boron, and mixturesthereof.
 24. A method for polymerizing an olefin comprising contactingan olefin with the olefin polymerization catalyst system of claim 23.25. The method of claim 24, wherein the olefin is ethylene, propylene,1-butene, 2-pentene, 1-hexene, 1-octene, styrene, 1,3-butadiene,norbomene, each of which may be substituted or unsubstituted, ormixtures thereof.
 26. The method of claim 25, wherein the olefin isethylene or 1-hexene.
 27. The method of claim 24, wherein at least oneof R¹-R¹¹ is selected from the group consisting of —C(halide)₃,CH(halide)₂ and —CH₂(halide).